Engine operation and compositions therefor



Dec. 8, 1964 J. E. BROWN ENGINE OPERATION AND COMPOSITIONS THEREFORFiled Oct. 16, 1959 FIGURE I IN V EN TOR.

' JEROMEE BROWN United States Patent 3,16%,592 ENGENE @PERATIGN ANDCGMPGdlTlGN THERAFQR Jerome E. Brown, Detroit, Mich assignor to EthylCorporation, New York, N.Y., a corporation of Virginia Filed Get. 16,1959, Ser. No. 847,618 11 Claims. (Cl. 252-49.?)

This invention relates to a method of operating a spark ignitioninternal combustion engine which utilizes novel compositions of mattercontaining certain nonionic metal polycarbonyl compounds which enable anengine to give knock-free performance and which possess numerousbenefitsin connection with improved combustion characteristics and thealleviation of modern day engine problems.

Concurrent with the development of the modern high eficiency, highcompression ratio, internal combustion engine of the spark ignitiontype, it was necessary to develop fuels which would permit theknock-free operation required to utilize most effectively these advancesin engine design. The approach to this problem has been in twodirections. On the one hand, improvements in refining operations havebeen undertaken to provide hydrocarbon fuels, wherein the ingredients ormixtures thereof possess high antiknock quality. There exists, however,a limit, depending on a number of factors, beyond which the fuels cannotbe econonncflly improved. 0n the other hand, additives have beenprovided for such fuels whereby a further increase in the antiknockquality of the mixture is produced.

The most successful antiknock additive from a practical standpoint hasbeen tetraethyllead. From time to time, a number of other antiknockmaterials have been proposed, but none of them has attained commercialsignificance in this country.

It is an object of this invention to provide an improved method foroperating an internal combustion engine. Another object is'to providenew compositions of matter. A more specific object is to provide newgasoline compositions. It is also an object of this invention to providea gasoline containing certain metal polycarbonyl antiknock compounds ormixtures of such compounds which possess greatly reduced wear causingcharacteristics. A still further object is to provide gasoline suitablefor use in high efiiciency, spark ignition internal combustion enginesrequiring a fuel of high antilmock quality. Still another object is toprovide a lubricating oil which acts to reduce the octane requirement ofan internal combustion engine. Among the other objects of this inventionis the alleviation of engine problems including octane requirementincrease, spark plug ionic manganese polycarbonyl compounds or mixturesof said manganese polycarbonyl compounds as antiknock agents.

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Thus, among the important compositions contemplated by the presentinvention are included a hydrocarbon fuel of the gasoline boiling rangefor use in spark ignition internal combustion engines containing a smallamount of non-ionic manganese polycarbonyls of the type definedsufiicient to improve the antiknock properties of said hydrocarbon fuel.For most purposes this amount of manganese compound will range fromabout 0.01 gram to about 6 grams of manganese per gallon of fuel.

In a preferred embodiment of the invention the amount of manganesecompound is regulated so as to be equivalent to from 0.2 gram to 4 gramsof manganese per gallon. More specifically, the present inventioncontemplates a hydrocarbon of the gasoline boiling range for use inspark ignition internal combustion engines con taining substantially1.77 grams of manganese in the form of a non-ionic manganesepolycarbonyl of the type defined per gallon of fuel. Furthercompositions which are contemplated by the present invention includeantiknock fluids which consist of organolead antiknock agents, usuallyalkyllead compounds such as tetraethyllead, together with non-ionicmanganese polycarbonyls of the type defined. Also within the purview ofthe invention are gasolines containing mixtures of said organeleadcompounds and said manganese polycarbonyls. Both the fuels and theantiknock fiuids may contain additional ingredients such as halogenatedhydrocarbon scavengers, phosphorus deposit modifying compositions,antioxidants such as alkylated phenols and the like. The presentinvention also embraces the process of obtaining improved operatingcharacteristics. of a spark ignition internal combustion engine whichcomprises operating said engine on a fuel composition which consists ofa hydrocarbon fuel of the gasoline boiling range containing a smallamount of non-ionic manganese polycarbonyl sufiicient to improve theantiknock properties of said hydrocarbon fuel.

Among the manganese carbonyl compounds suitable for use in the presentinvention are those which have the empirical formula R Mn(CO) where R isan organic radical, x is l and y is 5. These compounds and theirusefulness as antiknock agents are described in my copendingapplication, Serial No. 683,759, now Patent Number 2,913,413, filedSeptember 13, 1957, of which this application is a continuation-in-part.Application Serial No. 683,759 is in turn a continuation-in-part of myearlier copending application, Serial No. 645,828, now abandoned. R ismost preferably a monovalent hydrocarbon radical, such as an alkyl oraryl radical, or a monovalent acyl radical. Examples of these compoundsinclude methyl manganese pentacarbonyl, benzoyl manganese pentacarbonyl,phenyl manganese pentacarbonyl, acetyl manganese pentacarbonyl, and thelike. These and other manganese polycarbonyl compounds exhibitextraordinary antiknock effect and other unexpected properties whichrender them of interest as commercial antiknock agents.

The relative size of the organic radical in the manganese carbonylcompounds, while not too important, is best limited to .thosehaving from1 to about 20 carbon atoms, as it is found that these are best suited tothe practice of this invention. Compounds having organic groupscontaining from 1 to 13 carbon atoms are preferred as these compoundsare found to best combine the qualities of volatility and inductibilitywhich are prerequisites to proper functioning as gasoline additives.

Compounds having the formula RMn(CO) where the 3 R represents an organicradical from the group consisting of organic hydrocarbon radicals andorganic oxygen containing radicals, are conveniently prepared frommanganese carbonyl in an ethersolution. Manganese carbonyl is firstconverted to an alkali metal salt such as the sodium salt by treatingthe solution with an alkali metal present by an alkali metal dispersionor amalgam.

The alkali metal salt is then reacted with an alkylating agent such as adialkyl sulphate to form an alkyl manganese pentacarbonyl.-Alternatively, the alkali metal salt of manganese carbonyl is reactedwith an acyl halide to form an acyl manganese pentacarbonyl compound.These acyl manganese pentacarbonyl compounds are converted to thecorresponding lower alkyl or aryl manganese pentacarbonyl compounds bypyrolysis accornpanied by the loss of CO at elevated temperatures. Thus,phenyl manganese pentacarbonyl is conveniently produced by the pyrolysisof benzoyl manganese pentacarbonyl.

The lowest molecular weight compound having the formula RMn(CO) ismethyl manganese pentacarbonyl which is a crystalline solid melting atabout 95 C. and which is highly volatile and soluble in gasoline.Another compound of this class is benzoyl manganese pentacarbonyl, alsoa soluble crystalline solid, which melts at about 38 C. Propyl manganesepentacarbonyl and acetyl manganese pentacarbonyl are otherrepresentative members.

It is essential that the manganese polycarbonyl compounds-used in thepractice of this invention be'nonionic in nature in order that theyproduce the desired efiect. For example, ionic manganese carbonylcompounds such as those having halogen bonded directly to manganese arenot suiiiciently volatile to be readily inductible into the cylinders ofa multi-cylinder engine using a manifold type intake valve. Thesecompounds are unable to give the benefits attributable to non-ionicmanganese polycarbonyl compounds.

An unexpected feature of this invention is that the nonionic manganesepolycarbonyls are among the most efiective antiknock agents tested todate. This is particularly surprising when it is considered thatmanganese is located in the Periodic Table next to the element chromium.Chromium carbonyl exhibits a pro-knock effect when employed as agasoline additive for use in a spark ignition internal combustionengine. 7

Even when a compound has exceptional antiknock activity, the chances ofits becoming a useful product remain extremely remote. This is due tothe fact that many other properties must be taken into consideration dueto the excessive engine wear caused by their use. As a further example,many aromatic amines exhibit antiknock activity, but their use is notfeasible due to the fact that they exude a particularly objectionableodor.

Therefore, to be commercially successful, an antiknock must possess manyauxiliary properties in addition to outstanding antiknock activity. Anycompound under con sideration must undergo extensive tests to insurethat it meets the important secondary qualifications.

It has been found that the non-ionic manganese polycarbonyl compoundswhich are the subject of the present invention, possess all therequirements of a successful antiknock to a remarkable degree. That is,they not only exhibit outstanding antiknock effectiveness, but inaddition have the properties (including volatility, gasoline solubility,lack of gum forming tendencies, minimization of engine deposits andengine wear and susceptibility to preparation from available materials)required of commercial additives.

The fuels and lubricants used in todays high compression automotiveengines cause deposits to be formed during combustion. These depositswhich are derived from the fuels and lubricating oils and the additivestherein collect on essentialy all parts of the combustion chamberincluding the valves, the spark plugs and the cylinder Walls. Theformation of these deposits leads to several problems such as octanerequirement increase, deposit induced'ignition and spark plug fouling.These problems prevent maximum utilization of the potential of a fueland limit the designer from providing engines which will accomplish thisend.

Not only do the non-ionic manganese polycarbonyl compounds of thisinvention exhibit the properties required of a successful antiknock, butthey also have valuable and unexpected auxiliary efiects on theoperation of a spark ignition internal combustion engine. It has beenfound that these compounds when used either as fuel or lube oiladditives, minimize octane requirement increase and deposit inducedignition and increase the spark plug life of the modern high compressionspark ignition internal combustion engine.

An important embodiment of this invention is gasoline containing, inamounts sufiicient to improve the octane quality thereof, a' non-ionicmanganese polycarbonyl compound which is soluble in the-gasoline. It hasbeen found that non-ionic manganese polycarbonyl compounds are ofoutstanding effect as antiknock agents. The amount of the manganesepolycarbonyl compound present in the compositions of this invention isregulated such that at least about 0.01 gram of manganese is present pergallon of the finished gasoline, and ordinarily up to about 6 grams ofmanganese per gallon is provided. In a preferred embodiment the amountof manganese polycarbonyl is regulated to provide from 0.2 gram to 4.0grams of manganese per gallon of fuel.

The upper limit of beneficial use of the non-ionic manganesepolycarbonyl compounds is, as a practical matter, limited due to thefact that at high concentrations the magnitude of the octane numberbenefit obtainable per unit weight of compound decreases to some extent.Thus, the most beneficial antiknock effect of the nonionic manganesepolycarbonyl compound is realized' when these compounds are employed inconcentrations such that there is from about 0.03 to about 10 grams ofmanganese per gallon of the finished gasoline. At higher concentrationsthe antiknock effect per unit weight is diminished, and the otherbeneficial effects are also reduced. When used as a primary additive,the best results are obtained when from about 0.01 to about 6 grams ofmanganese are present in the gasoline.

As the non-ionic manganese polycarbonyl compounds find outstanding andunexpected utility as additives to both gasoline and crankcaselubricating oil, this invention gives rise to novel compositions ofmatter comprising a liquid hydrocarbon mixture useful in a sparkignition internal combustion engine, which mixture contains a non-ionicmanganese polycarbonyl compound of the type defined in amount sufiicientto improve the combustion characteristics of the engine. 7

The non-ionic manganese polycarbonyl antiknock agents of this inventionare also conveniently introduced into the cylinders of an internalcombustion engine by utilizing a separate system of supply inconjunction with the system which supplies fuel to the cylinders. Thus,the non-ionic manganese polycarbonyl compounds are supplied to thecylinders by atomizing, vaporizing or directly spraying the compound ora solution thereof, directly into the cylinders or into the intakemanifold which supplies the cylinders with fuel. Introduction of thenon-ionic manganese polycarbonyl compound into the manifolding systemmay be. acomplished either prior or subsequent to carburetion orinjection of the gasoline. When the non-ionic manganese polycarbonylcompound is a solid, it is often possible to vaporize it by passing astream of air over or through a supply of the compound. When thecompound is a liquid, it is conveniently supplied to the intake manifoldthrough a wick which is supplied from a reservoir of the liquid. 7

FIGURE 1 is illustrative of a method of introducing a non-ionicmanganese polycarbonyl compound into a combustion chamber of an internalcombustion engine having a plurality of combustion chambers equippedwith movable pistons wherein the walls of the chambers are lubricatedwith a crankcase lubricating oil and wherein gasoline is introduced intothe combustion chamber and ignited and the products of combustion actupon the pistons and produce a driving force. With reference to FIGURE1, the numeral 11 generally represents a cylinder and cylinder head of amulti-cylinder spark ignition internal combustion engine which containsa piston 11, combustion chamber 12, spark plug 13 which is under theinfluence of an ignition system (not shown), intake valve 14 and intakeport 15 through which gasoline and combustion air are supplied by acarburetion system (not shown), an exhaust valve 16 and an exhaust port17. These components make up the basic parts required in a conventionalfour-cycle spark ignition internal combustion engine.

To effectively conduct the process of tais invention, a non-ionicmagnanese polycarbonyl compound is conveniently injected into thecombustion chamber 12 by the utilization of a separate system whichconsists of a supplemental opening 18 which has fitted thereto a valve19 shown for purposes of illustration as a poppet valve held closed by aspring 20 and having an elongated stem 21 which places the valve underthe influence of a solenoid 22. The solenoid 22 is conveniently arrangedto be under the influence of a set of breaker points (not shown)coordinated with the ignition system of the engine so that the valve 19will be open during the intake stroke of the piston 11 for a timesuihcient to permitthe required amount of non-ionic manganesepolycarbonyl compound to enter the combustion chamber 12. The non-ionicmanganese polycarbonyl compound is supplied through the opening 18 bymeans of a vaporizing system 23 which terminates in an inlet port 24through which the valve stem 21 operates by means of the aperture 25.The valve stem 21 is sealed in the aperture 25 in any convenient manner.To supply a non-ionic manganese polycarbonyl compound as a vapor to thecombustion chamber 12 through the opening 18, a reservoir 26 of anyconvenient form contains a supply of manganese polycarbonyl compound toa convenient level 27. The container 26 is fitted with a means forpassing vaporizing gas through the manganese poly carbonyl compound asshown by the conduit 28 which is attached to an opening 29 in thecontainer 26. Back-up in the conduit 28 is prevented by any convenientmeans, such as a diaphragm valve 3G. To the upper portion of thecontainer 26 is attached a plurality of conduits 31 corresponding to thenumber of cylinders in the engine. The conduits 31 terminate in theinlet port 24. A vaporiz ing gas, such as nitrogen, air, carbon dioxideand the like, supplied from any convenient means such as a compressor ortank (not shown) through the conduit 28 passes through the manganesepolycarbonyl compound 27 and carries the compound as a vapor through theconduit 31 to the inlet port 24 where at the appropriate time it passesthrough the aperture 18 into the combustion chamber 12 where it mixeswith the gasoline and combustion air and improves the combustion whichtakes place under the influence of spark plug 13 at the end of thecomprcssion stroke of the piston 11. The manganese polycarbonyl compoundshown at 27 may be in the form of a solid such as methyl manganesepentacarbonyl or may be a liquid which contains a non-ionic manganesepolycarbonyl which may be blended with an antiknock fluid containinghalogen scavenger material and an organolead antiknock agent such astetraethyllead.

Fuels containing organolead antiknock agents ordinarily contain, inaddition to the antiknock agent, corrective agents commonly termedscavengers. Thus, when organolead antiknock agents are present in thecompositions of this invention, it is desirable to include therewithsuch scavengers. These scavengers consist of organo bromine and/0rchlorine compounds such as ethylene dibromide, ethylene dichloride andlike material. They function to inhibit the build-up of lead deposits onthe interior surface of internal combustion engines.

Halogen containing hydrocarbons are useful as scavengers in conjunctionwith the manganese polycarbonyl antiknock agents and are convenientlyblended therewith to form fluids which are added to gasoline to give thebenefits of this invention. These fluids also may contain small amountsof such hydrocarbon solvents as kerosene as well as dyes, antioxidantsand the like. The proportion of halogen in such compositions is adjustedsuch that an atom ratio of halogen to manganese of from about 0.221 upto 12:1 is achieved. However, the octane enhancement of the manganesepolycarbonyl compounds is realized even in the absence of suchscavengers.

Organolead antiknock agents are commonly provided as fluids for additionto hydrocarbon fuels. These fluids ordinarily contain the organoleadcompound and the halogen scavenger agents referred to above. Inaddition,

' these fluids also often contain solvents comprising mixtures ofhydrocarbons as well as antioxidants and the like. invention is theprovision of an antiknock fluid comprising an organolead compound and amanganese polycarbonyl compound. These fluids are convenientlyblendedwith hydrocarbon fuels to prepare the improved fuels to this invention.

Because of the property inherent in the manganese polycarbonyl compoundswithin the scope of this invention of being highly soluble in gasoline,such blending operations present little or no difiiculties. It isgenerally necessary only to add the requisite quantity of an improvedantiknock fluid of the present invention to gasoline; and, by stirring,shaking or otherwise mechanically agitating these components,homogeneous improved fuel compositions are obtained. As a result of thehigh solubility of the antiknock fluids of this invention in gasolinesuch fluids can be utilized in any commercially available gasolineincluding straight run, catal ytically cracked, catalytically reformedand thermally cracked base stocks and likewise, blends thereof.

in order to illustrate the utility and some of the commercial advantagesof employing the manganese carbonyl compounds used in the practice ofthis invention, a great number of tests have been conducted. The resultsof some of the most significant are presented below.

A most important feature of the present invention is the outstandingantikrrock activity'exhibited by the non-ionic manganese polycarbonylcompounds.

To demonstrate this antiknock effectiveness, tests were Thus, anothervariant within the purview of this 4 TABLE I Antiknock Efiectiveness ofCompounds of This Invention H. The initial boiling points (BF) and finalboiling 'Oetane r F E Numbgr of Mn, Resulting points (1 B?) o thegasonnes used are mdicated as Well AddltlVB p s as the particularmanganese polycarbonyl compounds and additive their concentrations interms of grams of manganese per gallon of gasolme. Other such improvedgasoline com- IMethyl manganese pentaearbonyl 91.8 0.18 93. 1 PQSitionswill be PF to one Skilled in the IMethyl manganese pentacarbonyL. 91.80.36 93.8 10 IMethyl manganese pentaearbonyl 01. S 1. S16. 0 Methylmanganese pentacarb0nyl 91. 8 2.0 97. 1 Methyl manganese pentaearbonyL.91.8 3.0 99.9 TABLE II lgiethyil manganese pentaeaigionyiln 91. 8 0. 599-1. G

enzy manganese pentacar ony 91.8 0.58 94.3 I 4 Acetylmanganesepentawbonylm 9L8 0 23 92. 9 Gasame Coma nzng Manganese PolycarbonylAcetyl manganese pentacarb0nyl 91. 8 0. 47 94. O Compounds Aeetylmanganese pentacarbonyl.-- 91.8 1.0 05.5 Trifluoroacetyl manganesepentacarbonyl 98. 7 0. S9. 4 Gasoline Grams Trilluoroacetyl manganesepenta- Example Manganese Polycarbonyl Mn per carbonyl 9S. 7 1. 0 101. 0Compound gal Trifluoroacetyl manganese penta- IBP FBP carbonyl es. 7 2.0 103. 3 Methyl manganese pentacarbonyl 80 1.02 94.3 20 Methyl manganesepentacarbony1 S0 2. 01 100.0 II 90 406 Phenylaeetyl manganese 0.01Propionyl manganese pentapentacarbonyl.

carbonyl 91.8 0.28 94.5 III 9a 390 Benzoyl manganese penta- 10.0Propionyl manganese pentacarbonyl.

carbonyl V 91.8 0.56' 95.3 IV 5'4 390 Aoetyl manganese ponta- 6.0 Phenylmanganese pentacarbonyL. 91. 8 0.50 94.4 carbonyl, Phenyl manganesepentacarbonyL- 91.8 1.0 05.9 V 8a 392 Ethyl manganese penta- 0.1

2D carbonyl. VI S9 385 Methyl manganese penta- 2.0 The antiknockproperties of manganese polycarbonyl VU 8 a l y a compounds are evenmore unexpected when it is con- 9 g z f pcma v sidered that some othercompounds of manganese are in- VIII 9 390 ni y s p 18 effective. Forexample, manganese naphthenate exhibits m on} a slight pro-knockquality. 7

The following examples are illustrative of the novel gasolines,lubricating oils and antilmock fluids which are EXAMPLES IX XIX withinthe Scope of thls mvennon' Table 111 illustrates typical gasolines ofthis invention EXAMPLE I V which contain a non-ionicmanganescpolycarbonyl com- A typical method of providing fuelscontaining a dispound in conjunction with an organolead compound. solvedmanganese polycarbonyl compound is as follows: The organolead antilmockswhich are ingredients of To a gasoline hav ng a final boiling point of406 in a certam of the compositions of this invention are prefervesselprovided with an agitator is added 6.29 parts of ably hydrocarbon leadcompounds such as tetraphenylethyl manganese pen-taoarbonyl per gallonof the gaso- 40 lead, tetratolyllcad and particularly tetraalkyllead,cornline. After agitating the mixture for approximately fifteen poundssuch as tetramethyllead, tetraethyllead, tetraprominutes, the ethylmanganese pentacarbonyl is completely pyllead, and the like.Tetraethyllead is preferred. In dissolved and uniformly distributedthroughout the fuel. general, the amount of organolead antiknock agentis se- This is demonstrated by analysis of a portion of the fuel lectcdso that its content of the gasoline is equivalent to for manganese,which shows the fuel to contain 1.77 grams about 0.1 to about 8 grams oflead per gallon of gaso of manganese per gallon of fuel mixture. line.

7 TABLE III EXAMPLES IIVIII Other improved gasoline compositions of thisinvention prepared as in Example I are illustrated in Table ImprovedGasolines Containing a Lead Amiknock Agent and a N0n-0nic ManganesePolycarbonyl Compound Gasoline M- .ga- Grams Scavenger Example ManganesePolyearhenyl nese, Lead Antilmoek of Pb Scavenger Cone, Per- Gravity,Additive g./ al. Agent per gal. gJgal. cent FBP API Benzyl man anesepenta- Ethylene dichloride- 1.48 426 61.4 carbon. 0.20 Tctraethylleadnu3.17 {gg k g fi? g L5 Trifiuorometh lman anese t yene ic ori e 1.48 426pentaearbon yl b t {Etlgylene Sibfipmiale--. 1.5

. Meth l man' mese en aa t yene ie ori e 1.48 426 carb onyl. & p Etylene dibromide 1.5 390 59.0 p-Octyl benzyl manganese 2.4Tetramethyllead 2.0 Dibromebutane 2.1

pentaearoonyl. 366 54. Nonoyl mangmese penta- 4.0 Tetraphenyllead 0.05'

t t i I t il d in 'd 43 .ee 1 man anese en a- .myene ie on e. 380 54.4cartbonyL 0.03 Tet.ae..hylleed 3.00 Dibmmmmem L4 XV 420 61.4' Benzoylmangmese penta 8.0 Tetrabutylleed 0.1

carbonyl. XVI 416 63.2 Phenyl manganese penta- 0.9 Tetraethyllead 5.1

carbonyl. XVII 0.02 426. 61.4 Methyl mangwese penta 0.05 --.,do 0.95

- carbonyl. I XVIII 00.8 Ethyl manganese pent-a- 0.10 (lo 0.90

carbonyl. XL 0.001 395 58.6 Tolyl manganese penta- 0.30 do 2.70 do acarbonyl. I

Antiknock activity of mixtures of my manganese additives with organoleadantiknocks is shown in Table IV.

TABLE IV EXAMPLE XX To 11 parts of methyl manganese pentacarbonyl isAntiknock Efiectiveness of Mixtures Compounds of This Invention WithOrganolead Antl'knock Agents TEL=tetraethyllead. TML=tetramethyllead.

Other compositions of this invention comprising an improved gasolinecontaining a non-ionic manganese polycarbonyl compound are prepared in amanner similar to that described above and illustrated in Examples 1through XIX. Further, illustrative examples of the non-ionic manganesepolycarbonyl compounds utilized alone or in admixture in such improvedgasolines include propionyl manganese pentacarbonyl, phenyl manganesepentaoarbonyl, benzoyl manganese pentacarbonyl, benzyl manganesepentacarbonyl, m-ethylbenzyl manganese pentacarbonyl and the like.

Where halohydrocarbon compounds are employed as scavenging agents, theamounts of halogen used are given in terms of theories of halogen. Atheory of halogen is defined as the amount of halogen which is necessaryto react completely with the metal present in the antiknock mixture toconvert it to the metal dihalide, as, for example, lead dihalide andmanganese dihalide. In other words, a theory of halogen represents twoatoms of halogen for every atom of lead =and/ or manganese present. Inlike manner, a theory of phosphorus is the amount of phosphorus requiredto convert the lead present to lead orthophosphate, Pb (PO that is, atheory of phosphorus based on lead represents an atom ratio of two atomsof phosphorus to three atoms of lead. When based on manganese, a theoryof phosphorus likewise represents two atoms of phosphorus for everythree atoms of mangamess, that is sufficient phosphorus to convertmanganese to manganese orthophosphate, M11 (PO The scavenger compoundscan be halohydrocarbons both aliphatic and aromatic in nature, or acombination of the two, with halogens being attached to carbons eitherin the aliphatic or the aromatic portions of the molecule. The scavengercompounds may also be carbon, hydrogen and oxygen-containing compounds,such as haloalkyl others, halohydrins, halo esters, halonit-rocompounds, and the like. Still other examples of scavengers that may beused in conjunction with my manganese compounds either with or withouthydrocarbolead compounds are illustrated in US. Patents 2,398,281 and2,479,900-903, and the lii: Mixtures of different scavengers may also beused. These fluids can contain other components as stated hereinabove.

In like manner, manganese-containing fluids are prepared containing from0.01 to 1.5 theories of phosphorus in the form of phosphorus compounds.To make up the finished fuels, the concentrated fluids are added to thegasoline in the desired amounts and the homogeneous fluid obtained bymixing, agitation, etc.

added 5 parts of ethylene dichloride and the mixture agitated until ahomogeneous fluid results. The manganese to chlorine atom ratio in thisfluid is 1:12 and represents 6 theories of halogen based on themanganese.

In like manner, a fluid is prepared comprising benzyl manganesepentacarbonyl and ethylene dibromide in which the manganese to bromineratio is 1:6, representing 3 theories of bromine based on the manganese.Likewise, a fluid containing isobutyryl manganese pentacarbonyl,ethylene bromohydrin, and 2,3-dichloro 1,4-dimethylbenzene is preparedin such proportions that for every 75 atoms of manganese, there are oneatom of bromine and two atoms of chlorine, representing a total of 0.02theory of halogen.

The above fluids are added to hydrocarbon fuels in amounts so as toprovide improved fuels containing 0.015 gram, 0.25 gram, 1.00 gram, 6grams and 10 grams of manganese per gallon.

EXAMPLE XXI .To 8.0 parts of lead in the form of tetraethyllead in anantiknock fluid containing 0.5 theory of bromine as ethylene dibromideand 1.0 theory of chlorine as ethylene dichloride, wherein the theoriesof halogen are based upon the amount of lead present, is added 0.015part of manganose in the form of an equimolar mixture of benzylmanganese pentacarbon l and acetyl manganese penta carbonyl.

This fluid is then added to a commercial hydrocarbon fuel havin aninitial boiling point of 82 F. and a final boiling point of 420 F. in anamount so as to provide 8.0 grams of lead and 0.015 gram of manganeseper gallon.

EXAMPLE XXII A concentrated fluid is prepared as in Example XXcontaining kerosene, a blue dye, and 10 parts by weight of manganese asan equimoiar mixture of methyl manganese pentacarbonyl andbenzoylmanganese pentacarbonyl for every 0.02 part of lead in the formof dicthyldimethyllead. This fluid is then blended with a commercialhydrocarbon fuel having an initial boiling point of F. I

and a final boiling point of 394 F. in an amount suflicient to provide10 grams of manganese and 0.02 gram of lead per gallon- EXAMPLE XXIIITetraethyllead and manganese penfiacarbonyl are admixed so that theratio is 2.0 grams of lead as tetraethyl lead present for every 1.0 gramof manganese present l l as phenyl manganese pentaoarbonyl. Thiscomposition is found to possess superior antiknock and deposit modifying properties when added to gasoline.

' EXAMPLE YXIV such as passenger cars, trucks, buses and the like,amounts 7 of any of the compositions of this invention equivalent tofrom between about 0.1 and about 4.3 grams of lead per gallon aresatisfactory. It will be appreciated, however, that in most cases thelead content of such improved fuels is preferably from between about1.06 and about 3.17 grams of lead per gallon which, when the organoleadconstituent of such fuels is tetraethyllead, is equivalent to frombetween about 1 and about 3 milliliters of tetraethyllead per gallon.When the improved gasolines of this invention are designed primarily foruse in aviation engines, somewhat greater concentrations can betolerated and are frequently preferred. In such instances, it isadvantageous to employ an amount of improved antiknock fluid of thisinvention equivalent to from between about 3.17 grams and about 6.34grams of lead per gallon. That is to say, when utilizing atetraethyllead-containin antiknock fluid of the present inven- 1 tion inan aviation fuel, amounts of such a fluid equivalent to from betweenabout 3 and about 6 milliliters of tetraethyllead per gallon aresatisfactory. Concentrations above these limits can be employed in bothmotor and aviation fuels, practical considerations being the primecriterion for establishing the upper concentration limit.

Use of antiknock fluids containing my non-ionic manganese polycarbonylsin addition to resulting in great convenience in storage, handling,transportation, blend- 4 and branched chain; olefins; cycloaliphaticscontaining paraffin or olefin side chains; and aromatic containingaliphatic side chains. The gasoline type depends on the base stock fromwhich it is obtained and on the method of refinin For example, it can bea straight run or processed hydrocarbon, including thermally cracked,catalytically cracked, reformed fractions, etc. When used forspark-fired engines, the boiling range of the components of gasoline canvary from zero to about 430 F., although the boiling range of the fuelblend is often found to be between an initial boiling point of fromabout 80 F. to 100 F. and a final boiling point of about 430 F. .Whilethe above is true for-ordinary gasoline, the boiling range is a littlemore restricted in the case of aviation gasoline. Specifications for thelatter often call for a boiling range of from about 82 F. to about 338F., with certain fractions of the fuel boiling away at particularintermediate temperatures. All commercial gasolines including all thoseembraced within the present invention, always contain a great number ofindividual hydrocarbon compounds as components and always have a finalboiling point of at least 300 F.

The gasolines in which the 'antiknock agents of this invention can beemployed often contain minor quan-;

titles of various impurities. One such impurity is sulfur which can bepresent either in a combined form as an i2 organic or inorganic compoundor as the elemental sulfur. The amounts of such sulfur can vary invarious fuels from about 0.003 percent to about 0.30 percent by weight.Fuels containing quantities of sulfur, both lesser and greater than therange of amounts referred to above, are also known.

For best results interms of spark plug life, the improved gasolines ofthis invention should contain at least 0.015 weight and 0.065 weightpercent of this element. These gasolines may also contain organoleadantiknock agents in the amounts specified above.

It will be apparent that the present invention is susceptible ofadditional variations. Some of these variants include the utilization inthe antiknock fluid embodiments of solubilizing agents, such askerosene, petroleum cuts or fractions, and in general various aromaticsolvents including those containing diphenyl and the like. In additionto this, various orgauolead stabilizers can be used in such embodiments.Among such materials are included styrene, naphthalene, lecithin,aminodiphenyl amines, phenyl-ot-naphthyl amine and analogous materials.Likewise, in both the antiknock fluid and antiknock fuel embodiments ofthis invention it is frequently advantageous to employ minor proportionsof antioxidants, particularly those of the phenylene diamine type aswell as the various alkyl phenols, such as 2,6-di-tertbutyl ph nol,2,4,6-tri-tert-butyl phenol, o-tert-butyl phenot, etc. A still furthervariant within the contemplation of this invention relates to theutilization of various organic dyestufis in the antiknock fluidembodiments of this invention, which materials serve primarily as ameans of product identification, although frequently the colorationproduced by suchdyestutfs imparts to the composition a degree ofstabilization against deterioration resulting from exposure to light.Furthermore, under certain circumstances benefits are to be obtained byutilizing as the scavengers in the diverse compositions of the presentinvention, organic halides possessing volatilities comparable to that ofthe organolead antiknock agent utilized. Such scavengers are describedin several of the patents cited hereinbefore.

The improved gasolines and fluids of the present in- Vention can beutilized in conjunction with other well known motor fuel adiuvants. Ofsuch materials, the various catalytically active substances, such asphosphorus compounds comprising various phosphates, phosphites,phosphonates and the like can thus be used in various embodiments ofthis invention. Other variants within the contemplation of thisinvention will be apparent to those skilled in the art.

The manganese polycarbonyl containingadditives of this invention may bemixed with antioxidants, such as alkylated phenols and amines, metaldeactivators, phosphorus compounds; antiknock agents, such as amines aswell as the alkyllead compounds mentioned above antirust and anti-icingagents, and wear inhibitors.

EXAMPLE XXV To 500 parts of a commercially available neutral crankcaselubricating oil is added a quantity of methyl manis stirred until ahomogeneous solution is obtained.

EXAMI E XYV II To 1000 parts of a mixed-base, solvent-refinedlubricatingv oil containing bright stock and which has an SAE 13viscosity grade of 20, an API gravity of 305 and a viscosity index of107.4 is added 0.05 percent manganese as benzyl manganese pentacarbonyl.

EXAMPLE XXVIII To 2162 parts of a wholly-distilled lubricating oilhaving an API gravity of 30.3", a viscosity index of 154.2 and an SAEnumber of W2O is added percent manganese as 'benzoyl manganesepentacarbonyl and the mixture is stirred until the benzoyl manganesepentacarbonyl is dissolved.

EXAMPLE XXIX To 216 parts of a wholly-distilled lubricating oil havingan API gravity of 29.1, an SAE number of l0W-30 and a viscosity index of138.9 is added 3 percent of manganese as phenyl butyryl manganesepentacarbonyl. The mixture is agitated until a homogeneous solution isobtained. 7

The lubricating oils used in the practice of this invention includethose fractions or blends of fractions from mineral oils which are usedfor lubricating purposes in the crankcase of an internal combustionengine. Lubricatin oil stock is usually considered to include all thedistillate obtainable from crude oils after the lower boiling fractionsand gas oils have been expelled, as well as some of the residues thatare left in the still when non-asphaltic crudes are distilled.

Generally lubricating oils are made from distilled fractions of a crude,but often these distilled fractions are combined with refined residium,such as bright stocks, to yield oils having excellent lubricatingqualities.

In addition to the non-ionic manganese pentacarbonyl compound, thelubricating oils of this invention may contain other additives. Theseother additives may include, for example, viscosity index improvers,detergents, corrosion inhibitors, metal deactivators, rust inhibitors,color stabilizers, pour depressants, emulsifiers, dyes, etc.

The non-ionic manganese poly carbonyl compounds used in the practice ofthis invention are prepared by various methods. Examples of these areindicated below.

EXAMPLE XXX Sodium manganese pentacarbonyl was prepared by treating a 5percent solution of manganese carbonyl in tetrahydrofuran with an excessof one percent sodium amalgam. After removal of the excess amalgam, thesupernatent liquid was treated with dimethyl sulfate and the resultingmixture, after standing overnight, was added to ice water and filtered.The precipitate was carefully dried in air and recrystallized forming alowboiling petroleum ether to give a 59.5 percent yield of methylmanganese pentacarbonyl.

Similar methods are employed to give excellent yields of benzylmanganese pentacarbonyl, benzoyl manganese pcntacarbonyl, styrylmanganese pentacarbonyl and the like.

EXAMPLE XXX I Benzoyl manganese pentacarbonyl is prepared in a mannersimilar to that describal in Example m by reacting benzoyl chloride withsodium manganese pentacarbonyl. The benzoyl manganese pentacarbonyl isgently heated to above 90 C. at which temperature a strong evolution ofgas is readily identified as carbon monoxide. When the gas evolutionceases, the remaining product is found on analysis to be phenylmanganese pentacarbonyl.

EXAMPLE XXXII When 8.7 parts of NaMn(CG) contained in 88 parts oftetrahydrofuran was treated with 3.2 parts of allyl chloride in anitrogen atmosphere and the resulting mixture cautiously heated toreflux for one hour, the mixture became turbid. Removal of the solventby distillation through a helix-packed column followed by distillationof the residues at reduced pressure gave a small yield of pale yellowliquid (allyl manganese pentacarbonyl) which solidifies on cooling toice bath temperature. The

compound has a boiling point of 32 C. at 2 millimeters. Analysis.Calcd.for C H MnO Mn, 23.3. Pound:

EXAMPLE XXXIII The sodium salt of 4.1 parts of manganese carbonyl wasreacted with three parts of acetyl chloride to give 3.5 parts of a paleyellow solid melting between 43 and 48 C. This material was purified bysuccessive sublimation to give 2.6 parts (a 51 percent yield) of pureacetyl manganese pentacarbonyl which melted at 54 to 56 C. Analysis ofthis compound showed that it contained 35.2 percent carbon, 1.28 percenthydrogen and 23.1 percent manganese. This corresponds very well with acalculated content of 35.32 percent carbon, 1.27 percent hydrogen and23.17 percent manganese for the formula CH COMn(CO) EXAMPLE XXXIV Asolution of 21.8 parts of sodium manganese pentacarbonyl was prepared byreacting 19.5 parts of manganese pentacarbonyl in 133 parts of anhydroustetrahydrofuran with an excess of freshly prepared one perpercent sodiumamalgum under nitrogen in a reaction vessel. This solution was thentransferred under nitrogen into a reaction vessel equipped with astirrer, dropping funnel, reflux condenser and nitrogen sweep. To thestirring solution from the funnel was slowly added 31.5 parts oftrifluoroacetic anhydride. An exothermic reaction occurred and a colorchange from opaque green/ brown to an almost transparent yellow tookplace. The solution was allowed to stir overnight at room temperatureafter which it was poured into ice water. A pale yellow solid separated,was filtered oil, and pressed dry. This yellow material, whenrecrystallized from carbon tetrachloride, gave 21.5 parts (81.4 percentyield) of white, flulfy crystalline product, perfiuoroacetyl manganesepentacarbonyl'having a melting point of 56.5- 57.5 C.

EXAMPLE XXXV Two samples of perfluoroacetyl manganese pentacarbonyl, 3.1parts and 2.0 pantsrespectively, were weighed separately into reactionvessels which were subsequently cooled and evacuated. The vessels werethen heated carefully to the temperature of hot water, and then rapidlyheated to 140 C. Both samples melted into yellow liquids and gasevolution was observed. Immediately after this evolution slowed, thevessels were cooled. Yellow-white solids covered the vessel interiorsand these were recrystallized from carbon tetrachloride and combined togive a total of 2.9 parts (63.0 percent yield) of white crystallineperfluoromethyl manganese pentacarbonyl, M.P. 8284 C. The infraredspectrum supported the proposed structure.

Analysis.-Calcd. for C F O Mn: Mu, 20.8. Found: Mn, 21.3.

When the non-ionic manganese polycarbonyl compounds used in the practiceof this invention contain an organic radical, such radical has, ingeneral, from 1 to about 20 carbon atoms. Thus, compounds suitable foruse in the process of this invention include pelargonyl manganesepentacarbonyl, dibutyl manganese tetracarbonyl, methyl manganesepentacarbonyl, and the like. These compounds have a molecular weightfrom about 194 to about 500.

When the organic group is a hydrocarbon radical, it preferably has from1 to about 13 carbon atoms and the manganese polycarbonyl compound whichcontains it has a molecular weight up to about 450. Examples of suchnon-ionic manganese polycarbonyl compounds inelude ethyl manganesepentacarbonyl, allyl manganese pentacarbonyl, phenyl manganesepentacarbonyl, p-hexyl benzyl manganese pentacarbonyl, and the like.

Likewise, when the organic group is an acyl radical or an acylatedhydrocarbon radical, it preferably contains up to about 13 carbon atomsand the non-ionic manganese polycarbonyl compound has a molecular weightup to about 465. Examples of these compounds include benzoyl manganesepentacarbonyl, stearoyl manganese pentacarbonyl, and the like.

The present invention resides in the discovery that the non-ionicmanganese polycarbonyl compounds are unexpectedly beneficial with regardto antiknock efiect when used in conjunction with the operation of aspark ignition internal combustion engine. The invention gives rise to anumber of embodiments including a novel process for operating such anengine by means of introducing a nonionic manganese polycarbonylcompound into the combustion chambers, and a number of novelcompositions which are of particular benefit in such a process. Thesenovel compositions include a liquid hydrocarbon mixture for use in suchan engine which mixture contains a nonionic manganese polycarbonylcompound. This liquid hydrocarbon mixture, as has been pointed out, maybe a gasoline or a lubricating oil. When the hydrocarbon 'is a gasolineit may contain an organolead antiknock agent and appropriatehalohydrocarbon scavengers in addition to the manganese polycarbonylcompound. Suitable organolead compounds include the alkyllead compound,tetraethyllead, which may be present in amount such that up to 6.34grams or more of lead are present per gallon of fuel. The atom ratio ofmanganese to lead may be from about 0.05 to 1 to 64 to 1, or, expresseddifferently, from about 1 to 20 to about 64 to 1. Applicablehalohydrocarbon scavengers include ethylene dichloride and ethylenedibromide.

Further novel compositions of particular benefit in conducting theprocess of this invention comprise antiknock fluids containing anon-ionic manganese polycarbonyl. Fluids containing halohydrocarbonscavengers along with the non-ionic manganese polycarbonyl compound arealso within the scope of this invention, as are fluids containingorganolead antiknock agents in addition to the non-ionic manganesepolycarbonyl compounds. Illustrative of such fluids are those containingmethyl manganese carbonyl and tetraethyllead such that the atom ratio ofmanganese to lead is from about 0.05 to about 64 to 1. These fluids areconveniently added to gasolines to give compositions containing up to6.34 o more grams of lead per gallon.

A variant in the practice of the present invention comprises the use ofa non-ionic manganese polycarbonyl compound wherein the organic group issubstituted with a non-ionic, non-reactive group.

Having fully described the nature of the presentinven tion, the needtherefor, and the best modes derived for carrying it out, it is intendedthat this invention be ganese as a non-ion-ic manganese polycarbonylcompound having the formula RMn(CO) wherein R is an organic radicalselected from the group consisting of hydrocarbon radicals and acylradicals and contains from 1 to about 20 carbon atoms.

2. The composition of claim 1 wherein R is an aliphatic hydrocarbonradical.

3. The composition of claim 1 wherein R is an aryl hydrocarbon radical.

4. The composition of claim 1 wherein R is an acyl radical.

5. Hydro-carbons of the gasoline boiling range containing from 0.01 toabout 10 grams of manganese per gallon as a non-ionic manganesepolycarbonyl compound having the formula wherein R is an organic radicalselected from the group consisting of hydrocarbon radicals and acylradicals and contains from 1 to about 20 carbon atoms.

6. The composition of claim 5 wherein R is an aliphatic hydrocarbonradical.

7. The composition of claim 5 wherein R is an aryl hydrocarbon radical.

8. The composition of claim 5 wherein R is an acyl radical;

9. The composition of claim 5 additionally containing from about 0.1 toabout 8.0 grams of lead per gallon as an organo-lead antiltnock agent.

10. An antiknock composition comprising a mixture of an organoleadantiknock agent and a non-ionic manganese polycarbonyl compound havingthe formula RMn(CO) 5 wherein R is an organic radical selected from thegroup consisting of hydrocarbon radicals and acyl radicals andcontaining from 1 to about 20 carbon atoms, wherein the atom ratio ofmanganese-to-lead is from about 1:20 to about 64:1.

11. Gasoline containing a small antiirnock quantity of methyl manganesepentacarbonyl, said antiknock quantity being between equivalent to about0.01 to about 10 grams of manganese per gallon.

References Cited in the file of this patent UNITED STATES PATENTS1,954,865 Danner Apr. 17, 1934 2,398,282 Bartholomew Apr. 9, 19462,434,578 Miller Jan. 13, 1948 2,763,617 Scott et al Sept. 18, 1956FOREIGN PATENTS 1,092,700 France Nov. 10, 1954 1,095,084 France Dec. 15,1954 7 OTHER REFERENCES Journal of the Institute of PetroleumTechnologists, vol. 13, l927-,pages 24-4 255.

Journal of the American Chemical Society, vol. 71, 1949, page 1899.

1. A LIQUID HYDROCARBON CRANKCASE LUBRICATING OIL CONTAINING FROM ABOUT0.05 TO ABOUT 10 WEIGHT PERCENT MANGANESE AS A NON-IONIC MANGANESEPOLYCARBONYL COMPOUND HAVING THE FORMULA